TW202116119A - Carrier-layer-included metal laminate base material and method for producing same, metal laminate base material and method for producing same, and printed wiring board - Google Patents

Abstract

The purpose of the present invention is to provide a carrier-layer-included metal laminate base material in which the high adhesion between an ultra-thin metal layer and a low-dielectric film is secured while maintaining the low adhesion between a carrier layer and the ultra-thin metal layer. A carrier-layer-included metal laminate base material 1A which comprises a low-dielectric film 20 and a three-layered carrier-layer-included metal foil 10 laminated on one surface of the low-dielectric film 20 and comprising a carrier layer 11, a release layer 12 and an ultra-thin metal layer 13, the carrier-layer-included metal laminate base material 1A being characterized in that the bonding strength between the ultra-thin metal layer 13 and the low-dielectric film 20 is larger than the peel strength between the carrier layer 11 and the ultra-thin metal layer 13.

Description

Metal laminated base material with carrier layer and manufacturing method thereof, metal laminated base material and manufacturing method thereof, and printed wiring board

The present invention relates to a metal laminate substrate with a carrier layer and a method for manufacturing the same, a metal laminate substrate and a method for manufacturing the same, and a printed wiring board.

Heretofore, as a member for forming fine wiring (fine pitch), a metal foil with a carrier layer has been known. This metal foil with a carrier layer is a laminate of a peelable carrier layer and an ultra-thin metal layer. It can be laminated with a hard substrate made of glass epoxy resin to obtain a metal laminate substrate with a carrier layer ( Laminated metal board). In addition, it is also known that instead of the aforementioned rigid substrate, a flexible polymer film is laminated, and it is used as a metal laminate base material for forming a flexible wiring board. In particular, as the polymer film, a film made of a low-dielectric polymer such as low-dielectric polyimide is used as a high-frequency circuit and is useful in the fifth-generation mobile communication system (5G).

In (Patent Document 1), it is disclosed that a copper foil with a carrier having an intermediate layer and an ultra-thin copper layer in this order is formed on one or both surfaces of the carrier. The aforementioned ultra-thin copper layer is on the surface of the copper foil, After the copper-containing primary particle layer is formed, a copper foil containing a secondary particle layer of a ternary alloy composed of copper, cobalt, and nickel is formed on the primary particle layer, and the color difference system described in the Japanese Industrial Standard JISZ8730 When measuring the color difference of the roughened surface, the color difference Δa* value from white is 4.0 or less, and the color difference Δb* value is 3.5 or less copper foil with copper foil for high frequency circuits. In addition, (Patent Document 1) also describes a copper-clad laminate board with a carrier in which a hard substrate such as a paper base phenol resin or a polymer film such as a liquid crystal polymer (LCP) and the aforementioned copper foil with a carrier are laminated. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2014-224318 A

[The problem to be solved by the invention]

In the aforementioned (Patent Document 1), when bonding a carrier-attached copper foil and a rigid substrate, the resin is impregnated into a base material such as glass cloth to prepare a glass fiber film in which the resin is hardened to a semi-cured state, and the copper foil is laminated It is applied to glass fiber film and heated and pressurized. In addition, when a polymer film is used instead of a rigid substrate, a base material such as a liquid crystal polymer is also bonded by laminating (thermocompression) of copper foil under high temperature and high pressure.

However, especially in the case of thermocompression attaching carrier metal foil to liquid crystal polymers suitable for high-frequency circuits, polyvinyl fluoride, low-dielectric polyimide and other low-dielectric films, consider the low dielectric For various characteristics such as the melting point of the electrical film, it is necessary to make the thermocompression bonding temperature 280°C or higher, or 300°C or higher. In such a temperature range, the peeling layer between the carrier layer and the ultra-thin metal layer may deteriorate. This is detrimental to the problem of the peelability of the carrier. On the other hand, if the temperature of thermocompression bonding is lowered in order to maintain releasability, there is a problem that the adhesion between the ultra-thin metal layer and the low-dielectric film decreases. That is, it has been difficult to maintain the peelability (low adhesion) between the carrier and the ultra-thin metal layer and to ensure the high adhesion between the ultra-thin metal layer and the low-dielectric film.

Here, the object of the present invention is to provide a metal laminated substrate with a carrier layer that maintains low adhesion between the carrier layer and the ultra-thin metal layer while ensuring high adhesion between the ultra-thin metal layer and the low-dielectric film, and其制造方法。 Its manufacturing method. In addition, an object is to provide a metal laminate substrate on which a low dielectric film and an ultra-thin metal layer are laminated, and a method of manufacturing the same. Furthermore, an object is to provide a printed wiring board that can be obtained from the aforementioned metal laminated base material and is suitable for use as a high-frequency circuit. [Means for problem solving]

The inventors of the present case have conducted an intensive review and found that when laminating a low-dielectric film and a metal foil with a carrier layer composed of a carrier layer, a release layer, and an ultra-thin metal layer, a specific bonding method is used. Separately controlling the bonding strength of the ultra-thin metal layer and the low-dielectric film, and the peeling strength of the carrier layer and the ultra-thin metal layer can solve the aforementioned problems, thereby completing the present invention. That is, the gist of the present invention is as follows.

(1) On at least one surface of the low dielectric film, a metal laminate base with a carrier layer composed of at least three layers including a carrier layer, a release layer, and an ultra-thin metal layer is laminated on a metal foil with a carrier layer material, The bonding strength of the ultra-thin metal layer and the low-dielectric film is higher than the peeling strength of the carrier layer and the ultra-thin metal layer of the metal laminated substrate with carrier layer. (2) The metal laminated substrate with a carrier layer as described in (1) above, wherein there is one or more metal-containing intermediate layer between the low dielectric film and the ultra-thin metal layer. (3) The metal laminate substrate with a carrier layer described in (2) above, the intermediate layer includes any selected from the group consisting of copper, iron, nickel, zinc, chromium, cobalt, titanium, tin, platinum, silver, and gold A metal or its alloy. (4) The metal laminated substrate with a carrier layer described in any one of (1) to (3) above, a low-dielectric film consisting of liquid crystal polymer, polyvinyl fluoride, polyamide, and low-dielectric polymer A low-dielectric polymer film selected by the group consisting of imines. (5) The metal laminated substrate with a carrier layer described in any one of (1) to (4) above, wherein the peel strength between the carrier layer and the ultra-thin metal layer is 0.15 N/cm or more and 0.5 N/cm or less. (6) The metal laminated substrate with a carrier layer described in any one of (1) to (5) above, wherein the bonding strength between the ultra-thin metal layer and the low-dielectric film is 2.0 N/cm or more. (7) The metal laminated substrate with a carrier layer according to any one of (1) to (6) above, and the release layer is an organic release layer or an inorganic release layer. (8) The metal-laminated base material with a carrier layer described in any one of (1) to (7) above, wherein the thickness of the ultra-thin metal layer is 0.5 μm or more and 10 μm or less. (9) The method of manufacturing a metal laminate substrate with a carrier layer described in (2) above, including: The step of preparing a low-dielectric film, and a metal foil with a carrier layer composed of at least three layers including a carrier layer, a release layer, and an ultra-thin metal layer, After activating at least one surface of the aforementioned low dielectric film by sputtering etching, the step of sputtering a metal-containing intermediate layer on the aforementioned surface, The step of activating the surface of the aforementioned intermediate layer by sputtering etching, The step of activating the surface of the aforementioned ultra-thin metal layer by sputtering etching, and The step of calendering and joining the aforementioned activated surfaces to each other at a reduction rate of 0-30% The manufacturing method of the metal laminated substrate with carrier layer. (10) The method for manufacturing a metal laminate substrate with a carrier layer described in (9) above, a low-dielectric film composed of liquid crystal polymer, polyvinyl fluoride, polyamide, and low-dielectric polyimide A low-dielectric polymer film selected by the group. (11) The method for producing a metal laminate substrate with a carrier layer as described in (9) or (10) above, after calender bonding, is heat-treated at 160°C or higher and 300°C or lower. (12) A metal laminate substrate, which is on at least one side of a low-dielectric film, an active thin metal layer is interposed with a metal-containing intermediate layer, and a combination of the aforementioned low-dielectric film and the aforementioned ultra-thin metal layer The bonding strength is 2.0 N/cm or more. (13) The metal laminated base material described in (12) above, wherein the intermediate layer contains any metal selected from the group consisting of copper, iron, nickel, zinc, chromium, cobalt, titanium, tin, platinum, silver and gold or Its alloy. (14) The metal laminated base material described in (12) or (13) above is laminated on the surface of the ultra-thin metal layer on the side of the intermediate layer and contains any metal selected from the group consisting of Cu, Co, and Ni Or the roughened particle layer of its alloy, and/or the anti-rust layer containing any metal or its alloy selected from the group consisting of Cr, Ni and Zn. (15) The metal laminated base material described in any one of (12) to (14), wherein the thickness of the ultra-thin metal layer is 0.5 μm or more and 10 μm or less. (16) A method of manufacturing a metal laminate substrate, which is a method of manufacturing a metal laminate substrate in which a metal-containing intermediate layer is interposed with a thin metal layer on at least one side of a low-dielectric film, A method for producing a metal laminate substrate including the step of peeling off the carrier layer of the metal laminate substrate with a carrier layer described in (2). (17) A printed wiring board in which a circuit is formed on the intermediate layer and the ultra-thin metal layer of the metal laminated base material described in any one of (12) to (15). This specification includes the contents disclosed in Japanese Patent Application Nos. 2019-154167 and 2020-013319, which are the basis for the priority of this case. [Effects of Invention]

According to the present invention, it is possible to maintain low adhesion between the carrier layer and the ultra-thin metal layer while ensuring high adhesion between the ultra-thin metal layer and the low-dielectric film by stacking the substrate with a metal layer with a carrier layer. In addition, it is possible to obtain a metal-laminated base material in which a low-dielectric film and an ultra-thin metal layer are laminated. This metal laminate substrate is suitable for high-frequency circuits.

Hereinafter, the present invention will be described in detail. Fig. 1 shows a cross section of a metal laminated substrate with a carrier layer according to the first embodiment of the present invention. The metal laminate substrate 1A with a carrier layer shown in FIG. 1 is a metal foil with a carrier layer 10 composed of a carrier layer 11, a peeling layer 12, and an ultra-thin metal layer 13, and a low-dielectric film 20 is sequentially layered It is roughly constituted by the product.

1 is not described, but on the surface of the ultra-thin metal layer 13 on the low dielectric film 20 side, a roughened particle layer, a rust preventive layer, a treated layer formed of a silane coupling agent, and the like may be laminated. These layers can be stacked in any type, or multiple layers can be stacked. The roughened particle layer may contain, for example, any metal selected from the group consisting of Cu, Co, and Ni, or an alloy thereof. Specifically, a cobalt-nickel alloy plating layer, a copper-cobalt-nickel alloy plating layer, and the like can be cited. In addition, the rust-preventing layer may contain, for example, any metal selected from the group consisting of Cr, Ni, and Zn, or an alloy thereof. Specifically, coating treatment of chromium oxide, coating treatment of a mixture of chromium oxide and zinc/zinc oxide, Ni plating, and the like can be mentioned. In addition, examples of the silane coupling agent include olefin-based silane, epoxy-based silane, acrylic-based silane, amino-based silane, and mercapto-based silane, but are not limited to these. The coating of the silane coupling agent can be performed by spraying by spray, coating by a coater, dipping, etc. as appropriate.

The carrier layer 11 has a sheet shape and functions as a support material or a protective layer for preventing wrinkles or breakage of the metal laminated substrate 1A with a carrier layer, and scratches on the ultra-thin metal layer 13. As the carrier layer 11, a foil or a plate made of copper, aluminum, nickel, alloys thereof (stainless steel, brass, etc.), a resin coated with a metal on the surface, or the like can be exemplified. The best is copper foil.

The thickness of the carrier layer 11 is not particularly limited, and can be appropriately set according to desired characteristics such as flexibility. Specifically, it is preferably about 10 μm or more and 100 μm or less. If the thickness is too thin, the handleability of the metal foil 10 with a carrier layer may be impaired, which is not preferable. That is, it may be deformed during processing, and the ultra-thin metal layer 13 may be wrinkled or cracked. In addition, if the carrier layer 11 is too thick, it has too high rigidity as a support material, and it may be difficult to peel off from the ultra-thin metal layer 13, which is not preferable. Furthermore, it also leads to an increase in the cost of producing the metal foil 10 with a carrier layer.

The peeling layer 12 reduces the peeling strength of the carrier layer 11, and also prevents heating when the metal foil 10 with a carrier layer and the low-dielectric film 20 are joined, which may cause a gap between the carrier layer 11 and the ultra-thin metal layer 13 The function of mutual diffusion. The peeling layer 12 may be any one of an organic peeling layer and an inorganic peeling layer. Examples of components used in the organic peeling layer include nitrogen-containing organic compounds, sulfur-containing organic compounds, carboxylic acids, and the like. Examples of nitrogen-containing organic compounds include triazole compounds, imidazole compounds, and the like. Examples of triazole compounds include 1,2,3-benzotriazole, carboxybenzotriazole, N',N'-bis(benzotriazolemethyl)urea, 1H-1,2,4 -Triazole and 3-amino-1H-1,2,4-triazole, etc. Examples of sulfur-containing organic compounds include thiol benzothiazole, trimer thiocyanate, 2-benzimidazole hydrogen thio group, and the like. As an example of a carboxylic acid, a monocarboxylic acid, a dicarboxylic acid, etc. are mentioned. In addition, as a component used for the inorganic release layer, for example, Ni, Mo, Co, Cr, Fe, Ti, W, P, Zn, chromate treatment film, etc. can be cited. In addition, the formation of the release layer 12 can be performed by bringing the component-containing solution of the release layer 12 into contact with the surface of the carrier layer 11 and fixing the components of the release layer to the surface of the carrier layer 11. When the carrier layer 11 and the component-containing solution of the release layer 12 are brought into contact, the contact can be performed by immersing in the solution containing the component of the release layer, spraying the solution containing the component of the release layer, flowing down the solution containing the component of the release layer, etc. , And then dry, etc. to be fixed. In addition, a method of forming a film of the components of the peeling layer 12 by a vapor-phase method such as vapor deposition or sputtering can also be adopted.

The thickness of the peeling layer 12 is typically 1 nm or more and 1 μm or less, preferably 5 nm or more and 500 nm or less, but it is not limited thereto. If the thickness of the peeling layer 12 is too thin, there is a problem that the separation from the ultra-thin metal layer 13 cannot be sufficiently performed, and the peeling is deteriorated. In addition, if the thickness is too thick, it may peel off, but the manufacturing cost increases. Therefore, it is appropriately set in consideration of these balances.

The metal constituting the ultra-thin metal layer 13 can be appropriately selected in accordance with the characteristics of the use or purpose of the carrier-layer metal-laminated base material 1A. Specifically, copper, iron, nickel, zinc, tin, chromium, gold, silver, platinum, cobalt, titanium, and alloys based on any of these can be cited. In particular, a layer of copper or copper alloy is preferable. By calendering and bonding these metals to the low-dielectric film 20, a flexible substrate for forming fine wiring can be obtained, for example.

The thickness of the ultra-thin metal layer 13 is 0.5 μm or more and 10 μm or less. Preferably, it is 1 μm or more and 7 μm or less. Here, the thickness of the ultra-thin metal layer 13 is obtained by taking an optical micrograph of the cross-section of the metal-laminated substrate 1A with a carrier layer, and measuring the thickness of the ultra-thin metal layer 13 at any 10 points in the optical micrograph. The average value of the value.

The manufacturing method of such an ultra-thin metal layer 13 is not particularly limited, and wet film formation methods such as electroless plating and electroplating methods, dry film formation methods such as sputtering and chemical vapor deposition, or a combination of these can be used And it is formed on the peeling layer 12.

In this embodiment, when comparing the bonding strength of the ultra-thin metal layer 13 and the low-dielectric film 20, and the peeling strength of the carrier layer 11 and the ultra-thin metal layer 13, the ultra-thin metal layer 13 and the low-dielectric film The bonding strength of 20 is greater. Thereby, when the carrier layer 11 is peeled from the ultra-thin metal layer 13, the peeling can be performed without wrinkling or cracking of the ultra-thin metal layer 13 or the like. However, if the value of the bonding strength between the ultra-thin metal layer 13 and the low-dielectric film 20 and the value of the peel strength between the carrier layer 11 and the ultra-thin metal layer 13 are too close, in fact, it may be difficult to peel the carrier layer 11. When it does not affect the interface between the ultra-thin metal layer 13 and the low-dielectric film 20, therefore, the bonding strength between the ultra-thin metal layer 13 and the low-dielectric film 20, and the peeling of the carrier layer 11 and the ultra-thin metal layer 13 The difference in strength is preferably 0.25 N/cm or more. More preferably, it is 0.5 N/cm or more, most preferably 1.5 N/cm or more. As a specific value of the bonding strength between the ultra-thin metal layer 13 and the low-dielectric film 20, and the peel strength between the carrier layer 11 and the ultra-thin metal layer 13, the bonding strength between the ultra-thin metal layer 13 and the low-dielectric film 20 It is preferably 2.0 N/cm or more. In addition, the peeling strength of the carrier layer 11 and the ultra-thin metal layer 13 should be greater than 0, preferably 0.5N/cm or less. In the area below about 0.05N/cm, due to the need to peel off the material (carrier layer 11, ultra-thin metal The rigidity of layer 13, low-dielectric film 20, other rust-preventing layers, etc.) itself may not be able to measure the correct peel strength. The peel strength of the carrier layer 11 and the ultra-thin metal layer 13 is preferably in the range of 0.15 N/cm or more and 0.5 N/cm or less. Moreover, in the measurement of the numerical value of the aforementioned bonding strength, first, a test piece with a width of 1 cm was prepared from the metal laminated base material 1A with a carrier layer. Then, after removing the carrier layer 11, electroplating is applied to the surface of the ultra-thin metal layer 13 (when the ultra-thin metal layer 13 is copper, for example, copper plating), a metal with a thickness of about 10-20 μm is formed on the surface of the low dielectric film 20 Layer (including ultra-thin metal layer 13). Next, after peeling a part of the aforementioned metal layer with a thickness of about 10-20 μm from the low-dielectric film 20, the low-dielectric film 20 is fixed to the support, and the aforementioned metal layer with a thickness of about 10-20 μm is relatively low The dielectric film 20 is stretched in the 90° direction. The force required for peeling at this time was used as the bonding strength (unit: N/cm). In addition, in the measurement of the aforementioned peel strength, first, a test piece with a width of 1 cm was prepared from the metal laminated base material 1A with a carrier layer. After part of the carrier layer 11 is peeled off, the low-dielectric film 20 including the ultra-thin metal layer 13 is fixed to the support, and the carrier layer 11 and the low-dielectric film 20 including the ultra-thin metal layer 13 are moved to 90 degrees. ° direction stretch. The force required for peeling at this time was used as the peeling strength (unit: N/cm).

In this specification, the term "the bonding strength of the ultra-thin metal layer and the low-dielectric film" refers to the bonding strength when the interface between the ultra-thin metal layer and the low-dielectric film is peeled off, and it also means that the bonding strength is due to the extremely thin metal layer and the low-dielectric film. The bonding strength when the inside of the thin metal layer is damaged and peeling off, and the bonding strength when the inside of the low-dielectric film is damaged and peeling off. Furthermore, the low dielectric properties of the ultra-thin metal layer are as described above. When the surface of the film side is laminated with a roughened particle layer, a rust preventive layer, a treatment layer using a silane coupling agent, etc. (collectively referred to as "treatment layer"), it also means bonding when the interface between the ultra-thin metal layer and the treatment layer is peeled off. Strength, the bonding strength when the interface between the treatment layer and the low-dielectric film is peeled, and the bonding strength when the inside of the treatment layer is broken and peeling. In addition, as in the second embodiment described later, the metal-laminated substrate with a carrier layer (FIG. 2), between the low-dielectric film 20 and the ultra-thin metal layer 13, there is a metal-containing intermediate layer 30 In this case, "the bonding strength between the ultra-thin metal layer and the low-dielectric film" also means the bonding strength when the ultra-thin metal layer is damaged and peeled off. In the case of the ultra-thin metal layer (the treatment layer exists, it is the treatment The bonding strength when the interface between the intermediate layer and the intermediate layer is peeled, the bonding strength when the interface between the intermediate layer and the low-dielectric film is peeled, the bonding strength when the peeling occurs due to the internal damage of the intermediate layer, and the bonding strength due to low Any of the bonding strengths when the inside of the dielectric film is destroyed and peeled off.

The low dielectric film 20 is laminated on the ultra-thin metal layer 13. As the material of the low-dielectric film 20, any low-dielectric polymer material that can be used as a flexible substrate is applicable. For example, the relative permittivity ε _r is 3.3 or less, and the value of the dielectric loss tanδ is 0.006 or less. Such materials are not limited to this. Specifically, it can be made of liquid crystal polymer, polyvinyl fluoride (fluorine-based resin such as polytetrafluoroethylene), polyamide, isocyanate compound, polyamide imide, polyimide, low-dielectric polyimide Materials such as imide, polyethylene terephthalate, and polyether imide are appropriately selected and used. Preferably, it is a liquid crystal polymer, polyvinyl fluoride, polyamide, or low-dielectric polyimide. The low-dielectric film 20 is a single-layer film or a laminate composed of multiple layers. In the case of multiple layers, as long as any one or more of the multiple layers is made of the aforementioned low-dielectric polymer material The layer can be. Layers other than the layer composed of a low-dielectric polymer material may be composed of various previously known materials such as epoxy resin. In addition, the liquid crystal polymer is an aromatic polyester resin that exhibits liquid crystal properties in a molten state and has a basic structure such as p-hydroxybenzoic acid.

The thickness of the low-dielectric film 20 can be appropriately set in accordance with the use of the metal laminate base material and the like. For example, when used as a flexible printed wiring board, the thickness is preferably 10 μm or more and 150 μm or less, and more preferably 10 μm or more and 120 μm or less. In addition, the thickness of the low dielectric film 20 before bonding can be measured with a micrometer or the like, and the average value of the thickness measured at 10 points randomly selected on the surface of the target low dielectric film. In addition, for the low dielectric film used, it is preferable that the deviation from the average value of the 10 points of the measured values is within 10% for all the measured values.

Next, the second embodiment of the present invention will be explained. Fig. 2 shows a cross section of a metal laminated substrate with a carrier layer according to a second embodiment of the present invention. In this embodiment, as shown in FIG. 2, a metal-containing intermediate layer 30 is provided between the ultra-thin metal layer 13 and the low dielectric film 20. The intermediate layer 30 may be one layer, or two or more layers may be laminated. Examples of the metal-containing intermediate layer 30 include a metal layer formed on the low-dielectric film 20 by vapor deposition, electroless plating, or sputtering.

2 is not shown, but similar to the metal laminated substrate with a carrier layer related to the first embodiment, roughened particles may be laminated on the surface of the ultra-thin metal layer 13 on the side of the intermediate layer 30 Layer or anti-rust layer, silane coupling agent layer, etc. These layers can be stacked in any type, or multiple layers can be stacked. The roughened particle layer may contain, for example, any metal or alloy selected from the group consisting of Cu, Co, and Ni, but it may not be limited to this. In addition, the anti-corrosion layer may contain, for example, any metal or alloy selected from the group consisting of Cr, Ni, and Zn, but it may not be limited to this.

The intermediate layer 30 preferably includes any metal or alloy selected from the group consisting of copper, iron, nickel, zinc, chromium, cobalt, titanium, tin, platinum, silver, and gold. In particular, when the ultra-thin metal layer 13 is copper or its alloy, the metal constituting the intermediate layer 30 is also preferably copper or an alloy containing copper such as a copper-nickel alloy. When the intermediate layer 30 is, for example, a Cu-Ni alloy, the ratio of Ni to Cu is preferably 10 to 90 at%. However, it is not limited to this. By providing these intermediate layers 30, not only can the surface of the ultra-thin metal layer 13 or the low-dielectric film 20 be protected, but also the adhesion between the ultra-thin metal layer 13 and the low-dielectric film 20 can be improved, and the intermediate layer 30 can be provided. Unique function (for example, function as an etching stop layer during etching process, etc.). The thickness of the intermediate layer 30 is not particularly limited as long as it can exhibit functions such as improving adhesion. Specifically, the thickness is preferably 5 nm or more and 200 nm or less, and more preferably 10 nm or more and 100 nm or less.

Secondly, related to the manufacturing method of the metal laminated substrate with a carrier layer of the present invention, particularly to manufacture the intermediate layer 30 having a metal between the low dielectric film 20 and the ultra-thin metal layer 13 as shown in FIG. 2 The case of the metal laminated substrate 1B with a carrier layer will be described as an example. The metal laminate substrate 1B with a carrier layer shown in FIG. 2 prepares a metal foil with a carrier layer 10 composed of a carrier layer 11, a peeling layer 12, and an ultra-thin metal layer 13, and a low-dielectric film 20. A metal-containing intermediate layer 30 is provided on the surface of the low dielectric film 20, and these can be obtained by bonding each other by various methods such as cold rolling bonding and surface activation bonding, and interlayer adhesion. In addition, the bonding and/or heat treatment under high pressure when manufacturing the metal laminated base material 1B with carrier layer may significantly change the structure of each layer of the metal laminated base material 1B with carrier layer before and after bonding and/or heat treatment. In addition, the characteristics of the metal laminated base material 1B with a carrier layer may be impaired, so it is better to select bonding/heat treatment conditions that can avoid such structural changes.

The best mode as a method of manufacturing the metal laminated base material 1B with a carrier layer will be described based on FIGS. 3A and 3B. First, as shown in FIG. 3A, after activating the surface 20a of the low dielectric film 20 by sputter etching (FIG. 3A(a)), a sputtering film is formed on the surface 20a of the low dielectric film 20 containing The intermediate layer 30 of metal. The conditions when performing sputtering film formation can be appropriately set according to the type of metal constituting the intermediate layer 30 or the thickness of the intermediate layer 30.

Next, as shown in FIG. 3B, the surface 30a of the intermediate layer 30 is activated by sputter etching, the surface 13a of the ultra-thin metal layer 13 of the metal foil with carrier layer 10 is activated by sputter etching, and these are joined by rolling. The activated surfaces (FIG. 3B( c )) can produce a metal laminated base material 1B with a carrier layer (FIG. 3B( d )). In addition, when the surface 13a of the ultra-thin metal layer 13 includes a roughened particle layer or a rust preventive layer, the surface of the roughened particle layer or the rust preventive layer is activated by sputter etching. At this time, by sputtering etching, the roughened particle layer or the anti-rust layer can be completely removed, or can be left without being removed. The reduction ratio during rolling and joining is 0 to 30%. Preferably it is 0-15%. The aforementioned surface activation bonding method can reduce the reduction rate, so that it can be bonded while maintaining the function of the release layer 12 (low adhesion). In addition, there is no wrinkling or cracking, and the thickness accuracy can be achieved.上Excellent ultra-thin metal layer 13. Furthermore, the fluctuation of the interface between the ultra-thin metal layer 13 and the intermediate layer 30 and the low dielectric film 20 can be reduced. Therefore, when the ultra-thin metal layer 13 and the intermediate layer 30 are patterned and etched to form a circuit, the thickness can be reduced. The precision is excellent and a precise circuit is obtained.

In addition, the surface 30a of the intermediate layer 30 before activation by sputter etching or the surface 13a of the ultra-thin metal layer 13 may be subjected to Ni plating or chromate treatment as needed to prevent oxidation or improve adhesion. , Silane coupling agent treatment, etc. In addition, the surface 13a of the ultra-thin metal layer 13 may be roughened as needed in order to improve the adhesion with the intermediate layer 30.

For sputtering and etching, for example, the metal foil with a carrier layer 10 to be joined or the low-dielectric film 20 provided with an intermediate layer 30 can be prepared and made into a long-size coil with a width of 100 mm to 600 mm to form the metal foil with a carrier layer. 10 or the low-dielectric film 20 is the grounded electrode, and 1MHz-50MHz alternating current is applied between it and the other electrodes supported by insulation to generate glow discharge, and the plasma generated by the glow discharge is The area of the exposed electrode is 1/3 or less of the area of the other electrode mentioned above. In the sputtering etching process, the grounded electrode is in the form of a cooling roll to prevent the temperature of the conveyed material from rising.

In the sputtering etching process, the surfaces to be joined of the carrier layer metal foil 10 or the low dielectric film 20 are sputtered with an inert gas under vacuum to completely remove the adsorbed substances on the surface and remove the oxide layer on the surface Part or all of. It is preferable that the copper oxide layer is completely removed. As the inert gas, argon, neon, xenon, krypton, etc., or at least one type of mixed gas containing these can be used. Although it depends on the type of metal, the adsorbed matter on the surface of the ultra-thin metal layer 13 or the intermediate layer 30 can be completely removed with an etching amount of about 1 nm, especially for the copper oxide layer, usually 5 nm to 12 nm ( SiO ₂ conversion) degree of removal.

The processing conditions of the sputtering etching can be appropriately set according to the type of the ultra-thin metal layer 13 or the intermediate layer 30, and the like. For example, it can be performed under vacuum with a plasma output of 100W to 10kW and a linear velocity of 0.5m/min to 30m/min. The degree of vacuum at this time is preferably higher in order to prevent re-adsorption of substances to the surface, for example, 1×10 ^-5 Pa to 10 Pa.

The surfaces of the ultra-thin metal layer 13 and the intermediate layer 30 that have been sputtered and etched can be pressure-bonded with each other by roll pressure bonding. The rolling line load for roll pressure bonding is not particularly limited. For example, it can be set in the range of 0.1 tf/cm to 10 tf/cm. However, when the metal foil 10 with a carrier layer or the low-dielectric film 20 provided with the intermediate layer 30 has a large thickness before joining, it may be necessary to increase the load of the rolling line in order to ensure the pressure during joining. Limited to this value range. On the other hand, if the load of the rolling line is too high, not only the surface layer of the ultra-thin metal layer 13 or the intermediate layer 30 but also the bonding interface will be easily deformed. Therefore, the thickness accuracy of each layer of the carrier-layer metal laminated base material 1B may be reduced. . In addition, when the load of the calender line is high, the processing strain applied at the time of joining may increase.

The reduction ratio at the time of crimping is 30% or less, preferably 8% or less, and more preferably 6% or less. In addition, the thickness may not change before and after crimping, so the lower limit of the reduction rate is 0%.

In order to prevent the bonding strength between the extremely thin metal layer 13 or the intermediate layer 30 from decreasing due to the resorption of oxygen to the surface of the ultra-thin metal layer 13 or the intermediate layer 30, it is best to use a non-oxidizing atmosphere, such as a vacuum or Ar, In an inert gas atmosphere.

In addition, the metal laminated base material 1B with a carrier layer obtained by pressure bonding can be further subjected to heat treatment as required. By heat treatment, the strain of the ultra-thin metal layer 13 or the intermediate layer 30 can be eliminated, and the adhesion between the layers can be improved. When this heat treatment is carried out at a high temperature for a long time, blisters may appear in the carrier layer 11 starting from the peeling layer 12, and the carrier layer 11 may be peeled off from the blisters, or conversely, the carrier layer 11 and the extremely thin metal The adhesiveness of the layer 13 is improved by mutual diffusion or the like, and it may be difficult to peel the carrier layer 11. In addition, depending on the combination of the ultra-thin metal layer 13 and the intermediate layer 30, an intermetallic compound is generated at the interface, and there is a tendency for adhesion (joining strength) to decrease. Therefore, the aforementioned heat treatment is performed at a temperature of 160°C or more and 300°C or less. More preferably, it is 180°C or more and 290°C or less. Alternatively, it is better not to perform heat treatment after rolling and joining. In addition, after the carrier layer 11 is peeled off/removed from the bonded metal laminate substrate 1B with a carrier layer, heat treatment may be performed within a temperature range in which intermetallic compounds are not formed at the interface between the ultra-thin metal layer 13 and the intermediate layer 30.

Next, the metal laminated base material of the present invention and its manufacturing method will be explained. FIG. 4 is a diagram showing the manufacturing steps of a metal laminated substrate related to an embodiment of the present invention. The metal-laminated base material 2 shown in FIG. 4 is roughly structured on one side of the low-dielectric film 20, and an active thin metal layer 13 is interposed with a metal-containing intermediate layer 30 interposed therebetween. The metal laminated base material 2 is the same as the metal laminated base material 1B with a carrier layer shown in FIG. 2 except that there is no carrier layer 11 and a release layer 12, and the structure of each layer is the same as that of the metal laminated base material 1B with a carrier layer. The composition of each layer is the same. This metal laminated base material 2 can be obtained from the metal laminated base material 1B with a carrier layer. That is, as shown in FIG. 4, a metal laminate substrate with a carrier layer 1B is prepared (FIG. 4(a)), and the carrier layer 11 and the release layer 12 of the metal laminate substrate with a carrier layer 1B are peeled off together (FIG. 4(b)) A metal laminated base material 2 with a three-layer structure can be obtained (FIG. 4(c)).

The manufactured metal laminate base material 2 has, for example, an extremely thin metal layer 13 having a thickness of 0.5 μm or more and 10 μm or less, and can be used as a metal laminate substrate (metal-laminated base material for making flexible circuit boards). Laminated board). In addition, the metal laminated substrate of the present invention is included on the surface of the ultra-thin metal layer 13 on the opposite side of the low dielectric film, and additional metal is laminated by electroless plating, electroplating (for example, copper plating), etc. The type of layer.

The metal laminated base material 2 can be used to obtain a printed wiring board on which fine circuits are formed. In the step of forming the circuit, the aforementioned additional metal layer may be formed only on the circuit part. Specifically, a conventionally known method such as a modified semi-additive method (MSAP method) or a semi-additive method (SAP method) can be appropriately used to obtain a printed wiring board. For example, the poles of the metal laminated base material 2 can be covered. The non-circuit part on the thin metal layer 13 is copper-plated to the uncovered part to form an additional metal layer, the mask is removed, and the ultra-thin metal layer 13 hidden by the mask is removed by etching to manufacture a printed circuit board. In addition, the "printed wiring board" of the present invention includes not only a laminate in which a circuit is formed, but also a laminate in which electronic components such as ICs are mounted after the circuit is formed.

The implementation patterns of the metal laminate substrate with carrier layer 1A in FIG. 1, the metal laminate substrate with carrier layer 1B in FIG. 2, and the metal laminate substrate 2 in FIG. 4 are for low dielectric films The case where the carrier layer metal foil 10 or the ultra-thin metal layer 13 is laminated on one side of 20 will be described, but it is not limited to this. That is, if necessary, an intermediate layer 30, an ultra-thin metal layer 13, a peeling layer 12, and a carrier layer 11 may be provided on both sides of the low dielectric film 20. By using the metal laminate substrates with these layers provided on both sides of the low dielectric film 20 with a carrier layer, a flexible printed wiring board in which circuits are formed on both sides of the low dielectric film 20 can be obtained. [Example]

Hereinafter, the present invention will be further described in detail based on examples and comparative examples, but the present invention is not limited to these examples.

(Example 1) First, prepare a metal foil with a carrier layer. On a carrier layer made of copper with a thickness of 18 μm, an ultra-thin copper layer with a thickness of 1.5 μm and roughened particles on the surface are provided via a peeling layer (organic peeling layer). Layer and anti-rust layer copper foil with carrier layer (MT18FL manufactured by Mitsui Mining & Smelting Co., Ltd.), and a liquid crystal polymer (LCP) film with a thickness of 25 μm as a low-dielectric film. After the surface of the LCP film is activated by sputtering etching, an intermediate layer (thickness of 40 nm) made of copper is formed by sputtering. Then, the surfaces of the ultra-thin copper layer and the intermediate layer are rolled and joined to each other to manufacture the target metal laminated substrate with a carrier layer. The wire load during crimping was 1.5tf/cm, and the reduction rate due to surface activation bonding was 2.2%. After rolling and joining, heat treatment at 240°C is performed.

(Example 2) As the metal foil with a carrier layer, a copper foil with a carrier layer (MT18FL manufactured by Mitsui Mining & Smelting Co., Ltd.) was used. On a carrier layer made of copper with a thickness of 18 μm, a release layer (organic release layer) was provided. There is an ultra-thin copper layer with a thickness of 1.5μm and a roughened particle layer and anti-rust layer on the surface. In addition, as the low-dielectric film, an LCP film with a thickness of 100 μm was used. After the surface was activated by sputtering etching, an intermediate layer (thickness of 40 nm) made of copper was formed by sputtering. Next, the surfaces of the ultra-thin copper layer and the intermediate layer are joined by rolling, and thereafter, heat treatment is performed to produce a metal-laminated base material with a carrier layer. The joining conditions are shown in Table 1. In addition, the reduction rate due to surface activation bonding was 2.5%.

(Examples 3 and 4) Except that the bonding conditions were changed as shown in Table 1, the same procedure as in Example 2 was carried out to produce a metal laminate substrate with a carrier layer. The reduction rates of Examples 3 and 4 are 2.5% and 3.5%, respectively.

(Example 5) As the low dielectric film and the intermediate layer, as in Example 1, an intermediate layer made of copper (thickness 40nm) was formed on the surface of the 25μm-thick LCP film by sputtering, and the bonding conditions were changed. Except as shown in Table 1, the same method as in Example 2 was carried out to produce a metal laminate substrate with a carrier layer. The reduction rate is 2.2%.

(Example 6) As the metal foil with a carrier layer, a copper foil with a carrier layer (JXUT-III manufactured by JX Nippon Mining & Metals Corporation) was used, and a release layer (inorganic release layer) was provided on a carrier layer made of copper with a thickness of 18 μm. There is an ultra-thin copper layer with a thickness of 3.0μm and the roughened particle layer and rust-preventing layer on the surface. Furthermore, the bonding conditions are changed as shown in Table 1, and the same procedure as in Example 5 is carried out to produce a metal laminate with a carrier layer. Substrate. The reduction rate is 4.3%.

(Example 7) As a low-dielectric film and intermediate layer, an intermediate layer made of copper (thickness 40nm) is formed on the surface of a low-dielectric polyimide (modified polyimide, MPI) film with a thickness of 25μm by sputtering. Except for ), the same procedure as in Example 4 was carried out to produce a metal laminate substrate with a carrier layer. The reduction rate is 2.2%.

(Example 8) As the metal foil with a carrier layer, a copper foil with a carrier layer (Prototype 1) was used. On a carrier layer made of copper with a thickness of 18 μm, an ultra-thin copper layer with a thickness of 2.0 μm was interposed with a release layer (inorganic release layer). The layer and the only rust-preventing layer (layer without roughening particles) on the surface, and the bonding conditions were changed as shown in Table 1, and the same procedure as in Example 6 was carried out to produce a metal laminated substrate with a carrier layer. The reduction rate is 2.2%.

(Example 9) As the metal foil with a carrier layer, a copper foil with a carrier layer (Prototype 2) was used. On a carrier layer made of copper with a thickness of 18 μm, an ultra-thin copper with a thickness of 5.0 μm was interposed with a release layer (organic release layer). The layer and the only antirust layer (no roughened particle layer) on the surface, and the bonding conditions were changed as shown in Table 1, and the same procedure as in Example 8 was carried out to produce a metal laminated substrate with a carrier layer. The reduction rate is 6.3%.

(Comparative example 1) Except that the bonding conditions were changed as shown in Table 1, the same procedure as in Example 5 was carried out to produce a metal laminate substrate with a carrier layer. The reduction rate is 2.2%.

(Comparative example 2) Except that the bonding conditions were changed as shown in Table 1, the same procedure as in Example 6 was carried out to produce a metal laminate substrate with a carrier layer. The reduction rate is 4.3%.

(Comparative example 3) Except that the bonding conditions were changed as shown in Table 1, the same procedure as in Example 5 was carried out to produce a metal laminate substrate with a carrier layer. The reduction rate is 2.2%.

(Comparative Example 4) Except that the bonding conditions were changed as shown in Table 1, the same procedure as in Example 6 was carried out to produce a metal laminate substrate with a carrier layer. The reduction rate is 4.3%.

(Comparative Example 5) First, prepare a metal foil with a carrier layer. On a carrier layer made of copper with a thickness of 18 μm, an ultra-thin copper layer with a thickness of 2.0 μm and roughened particles on the surface are provided via a release layer (organic release layer). Layer and anti-rust layer copper foil with carrier layer (MT18FL manufactured by Mitsui Mining & Smelting Co., Ltd.), and a liquid crystal polymer (LCP) film with a thickness of 25 μm as a low-dielectric film. Then, the copper foil with a carrier layer and the LCP film were joined by thermocompression bonding to produce a metal laminated base material with a carrier layer. The conditions of thermal compression bonding are shown in Table 2.

(Comparative Examples 6 and 7) Except that the conditions of thermocompression bonding were changed as shown in Table 2, the same procedure as in Comparative Example 5 was carried out to produce a metal laminate substrate with a carrier layer.

(Comparative Example 8) First, prepare a metal foil with a carrier layer. On a carrier layer made of copper with a thickness of 18 μm, an ultra-thin copper layer with a thickness of 3.0 μm and roughened particles on the surface are provided via a release layer (inorganic release layer). Layer and anti-rust layer copper foil with carrier layer (JXUT-III manufactured by JX Nippon Mining & Metals Corporation), and a liquid crystal polymer (LCP) film with a thickness of 25 μm as a low-dielectric film. Then, the copper foil with a carrier layer and the LCP film were joined by thermocompression bonding to produce a metal laminated base material with a carrier layer. The conditions of thermal compression bonding are shown in Table 2.

(Comparative Examples 9 and 10) Except that the conditions of thermocompression bonding were changed as shown in Table 2, the same procedure as in Comparative Example 8 was carried out to produce a metal laminate substrate with a carrier layer.

For the metal laminate substrates with a carrier layer obtained in Examples 1-9 and Comparative Examples 1-10, the bonding strength between the ultra-thin copper layer and the low-dielectric film, the peel strength between the carrier layer and the ultra-thin copper layer, and the And the total thickness. The measurement results are shown in Table 3.

As shown in Tables 1 and 3, when the heat treatment temperature is high (Comparative Examples 1 and 2) and when the heat treatment temperature is low (Comparative Examples 3 and 4), the low adhesion between the carrier layer and the ultra-thin copper layer cannot be considered. , High adhesion with ultra-thin copper layer and low dielectric film.

In addition, as shown in Tables 2 and 3, when the copper foil with a carrier layer and the low-dielectric film are joined by thermocompression bonding, the low adhesion between the carrier layer and the ultra-thin copper layer, and the extreme High adhesion between thin copper layer and low dielectric film. In particular, in Comparative Examples 6, 7, 9, and 10, the low-dielectric film was deteriorated and embrittled, and it was not suitable as a metal laminate base material for circuit formation. In addition, in Comparative Example 10, the carrier layer and the ultra-thin copper layer could not be peeled off.

In addition, for each peeled surface after the bonding strength measurement in Example 5, observation with a scanning electron microscope (SEM) and surface element analysis with EDX were performed. The scanning electron microscope image is shown in Figure 5. As a result of the analysis, it was confirmed that copper was not adhered to the peeling surface on the LCP side of Example 5. In addition, a part of the agglomerated broken LCP is attached to the ultra-thin copper layer side (the peeling surface is the intermediate layer). Therefore, it is obvious that the peeling is caused by both the internal destruction of the LCP and the peeling of the interface between the intermediate layer and the LCP.

(Examples 10-16) By removing the carrier layer from the metal laminate substrate with a carrier layer obtained in Examples 1-7, a metal having an ultra-thin copper layer with a thickness of 1.5 μm to 3.0 μm including a roughened particle layer and a rust preventive layer was produced. Laminated substrates.

(Examples 17, 18) By removing the carrier layer from the metal laminated substrate with a carrier layer obtained in Examples 8 and 9, an extremely thin layer with a thickness of 2.0 μm to 5.0 μm including only the rust preventive layer (not including the roughened particle layer) was produced The metal laminate base material of the copper layer.

With respect to the obtained metal-laminated base materials of Examples 10 to 18, the bonding strength of the ultra-thin copper layer and the low-dielectric film, the total thickness, and the thickness of the ultra-thin copper layer were measured. The measurement results are shown in Table 4.

The metal laminate substrates of these Examples 10-16 are composed of an ultra-thin copper layer, a roughened particle layer, an anti-rust layer, an intermediate layer (copper), and an LCP or MPI film. In addition, the examples 17 and 18 The metal laminate base material is composed of an ultra-thin copper layer, an anti-rust layer, an intermediate layer (copper) and LCP. For these metal laminated substrates, the element distribution state (Depth Profile) in the depth direction of Glow Discharge Optical Emission Spectroscopy (GDS) and Ogee Electron Spectroscopy (AES) can be measured or a transmission electron microscope (TEM) can be used. Observation of the cross-section to identify the layered state of each layer.

In addition, it is possible to form circuit patterns on the extremely thin copper layer of the metal laminate substrate with resists, etc., and use the modified semi-additive method (MSAP method) or semi-additive method (SAP method) to achieve low dielectric A fine circuit is formed on the electrical film. All publications, patents, and patent applications cited in this specification are incorporated into this specification by reference in their entirety.

1A: Metal laminated substrate with carrier layer 1B: Metal laminated substrate with carrier layer 2: Metal laminated base material 10: Metal foil with carrier layer 11: carrier layer 12: peeling layer 13: Very thin metal layer 13a: Surface of extremely thin metal layer 20: Low dielectric film 20a: Surface of low dielectric film 30: middle layer 30a: Surface of the middle layer

Fig. 1 is a cross-sectional view of a metal laminated substrate with a carrier layer related to the first embodiment of the present invention. Fig. 2 is a cross-sectional view of a metal laminated substrate with a carrier layer related to a second embodiment of the present invention. [FIG. 3A] is a diagram showing the manufacturing steps of the metal laminated substrate with a carrier layer related to the second embodiment of the present invention. [Fig. 3B] is a diagram showing the manufacturing steps of the metal laminated substrate with a carrier layer related to the second embodiment of the present invention. [Fig. 4] is a diagram showing the manufacturing steps of a metal laminated substrate related to an embodiment of the present invention. Fig. 5 is a scanning electron microscope (SEM) image of the peeling surface of the metal laminate substrate with a carrier layer of Example 5 when the ultra-thin copper layer and the low dielectric film are peeled off.

1A: Metal laminated substrate with carrier layer

10: Metal foil with carrier layer

11: carrier layer

12: peeling layer

13: Very thin metal layer

20: Low dielectric film

Claims (17)

A metal laminate substrate with a carrier layer, which is formed on at least one surface of a low-dielectric film, and a metal foil with a carrier layer formed by laminating at least three layers including a carrier layer, a release layer, and an ultra-thin metal layer , The bonding strength of the ultra-thin metal layer and the low-dielectric film is greater than the peeling strength of the carrier layer and the ultra-thin metal layer. Such as the metal laminated substrate with carrier layer of claim 1, wherein Between the low dielectric film and the ultra-thin metal layer, there is one or more metal-containing intermediate layer. Such as the metal laminated substrate with carrier layer of claim 2, wherein The intermediate layer includes any metal or alloy selected from the group consisting of copper, iron, nickel, zinc, chromium, cobalt, titanium, tin, platinum, silver, and gold. Such as the metal laminated substrate with carrier layer of any one of claims 1 to 3, wherein The low-dielectric film is a low-dielectric polymer film selected from the group consisting of liquid crystal polymer, polyvinyl fluoride, polyamide, and low-dielectric polyimide. Such as the metal laminated substrate with carrier layer of any one of claims 1 to 3, wherein The peel strength between the carrier layer and the ultra-thin metal layer is 0.15N/cm or more and 0.5N/cm or less. Such as the metal laminated substrate with carrier layer of any one of claims 1 to 3, wherein The bonding strength between the ultra-thin metal layer and the low-dielectric film is 2.0 N/cm or more. Such as the metal laminated substrate with carrier layer of any one of claims 1 to 3, wherein The peeling layer is an organic peeling layer or an inorganic peeling layer. Such as the metal laminated substrate with carrier layer of any one of claims 1 to 3, wherein The thickness of the ultra-thin metal layer is 0.5 μm or more and 10 μm or less. A method for manufacturing a metal laminate substrate with a carrier layer is the method for manufacturing a metal laminate substrate with a carrier layer described in claim 2, comprising: The step of preparing a low-dielectric film, and a metal foil with a carrier layer composed of at least three layers including a carrier layer, a release layer, and an ultra-thin metal layer, After activating at least one surface of the aforementioned low dielectric film by sputtering etching, the step of sputtering a metal-containing intermediate layer on the aforementioned surface, The step of activating the surface of the aforementioned intermediate layer by sputtering etching, The step of activating the surface of the aforementioned ultra-thin metal layer by sputtering etching, and The step of calendering and joining the aforementioned activated surfaces to each other at a reduction rate of 0-30%. Such as Claim 9 of the manufacturing method of a metal laminated substrate with a carrier layer, wherein The low-dielectric film is a low-dielectric polymer film selected from the group consisting of liquid crystal polymer, polyvinyl fluoride, polyamide, and low-dielectric polyimide. Such as claim 9 or 10 of the manufacturing method of a metal laminate substrate with a carrier layer, wherein After rolling and joining, heat treatment at 160°C or higher and 300°C or lower is performed. A metal laminate substrate, which is located on at least one side of a low-dielectric film, an active thin metal layer is interposed with a metal-containing intermediate layer, and the bonding strength of the aforementioned low-dielectric film and the aforementioned ultra-thin metal layer is Above 2.0N/cm. Such as the metal laminated base material of claim 12, where The intermediate layer includes any metal or alloy selected from the group consisting of copper, iron, nickel, zinc, chromium, cobalt, titanium, tin, platinum, silver, and gold. Such as the metal laminated base material of claim 12 or 13, where On the surface of the ultra-thin metal layer on the side of the intermediate layer, a layer of roughened particles containing any metal or alloy selected from the group consisting of Cu, Co, and Ni is laminated, and/or a layer containing Cr, Ni, and Zn An anti-rust layer of any metal or its alloy selected by the constituent group. Such as the metal laminated base material of claim 12 or 13, where The thickness of the ultra-thin metal layer is 0.5 μm or more and 10 μm or less. A method for manufacturing a metal laminate substrate, which is based on at least one side of a low dielectric film, an active thin metal layer is interposed with a metal-containing intermediate layer, and the metal laminate substrate with a carrier layer of the peeling request item 2 is included Of the aforementioned carrier layer of the material. A printed circuit board is formed on the middle layer and the ultra-thin metal layer of the metal laminated base material of any one of claims 12 to 15 to form a circuit.

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